KR101460185B1 - A core composition for an optical amplifiers - Google Patents

Abstract

The present disclosure relates to a core composition for optical waveguide devices, said core composition comprising:
(a) fluorine-substituted acrylic monomers;
(b) an erbium complex;
(c) cyclic structure-containing normal temperature liquid phase monomer;
(d) siloxane-based compounds; And
(e) a reaction initiator.

Description

[0001] The present invention relates to a core composition for optical amplifiers,

The present invention relates to the provision of a core composition for use in the formation of an optical waveguide device and its core layer.

In optical communication systems, there are optical fibers and optical waveguides as media for transferring optical signals. These layers are composed of an inner core layer and a cladding layer surrounding the core layer, and transmit the signal by causing total reflection of light toward the core having a higher refractive index than that of the cladding layer.

In the case of long distance transmission (about 40 ~ 80 km transmission) through optical fiber in optical communication system, the optical signal is reduced to about 1/10 to 1/100 due to scattering and absorption, and waveform distortion due to dispersion occurs. The optical signal is reduced by such attenuation and waveform distortion. In order to compensate for this, an optical signal must be formed in the middle of the core for the optical amplifier. Currently, erbium (Er) ions emitting in the 1.55 ㎛ band of the optical communication wavelength band are used as a core composition for optical amplifying devices, and erbium Doped fiber amplifier (EDFA) and erbium-doped waveguide amplifier (EDWA) have been developed for use in optical fiber amplifiers. EDFAs are tens of meters in size and are bulky and expensive, which leads to integration with other passive devices and the implementation of a complete optical network. In order to compensate for this problem, EDWA doped with erbium ions is commonly used as a core composition for an optical amplifier. Generally, EDWAs are used in a waveguide of several tens of centimeters, Since the composition efficiency must be obtained, the matrix material, silica, must be doped with a high concentration of erbium ions. However, silica, which is a conventional matrix material, is difficult to dope (add) a high concentration of erbium ions due to its low solubility in a rare earth ion complex such as erbium, requires a high temperature heat treatment process, There are disadvantages. Therefore, in advanced countries such as Japan, USA, and Europe, efforts are being made to develop EDWA using a polymer matrix instead of silica.

The optical waveguide is the most basic element among the various optical elements constituting the optical integrated circuit and is used not only for transferring the optical signal from one place to another but also partially modifying the structure of the optical waveguide, Demultiplexing, switching, and multiplexing by dividing or collecting the data. Recently, many techniques for realizing an optical waveguide on a flat substrate such as a printed circuit board have been developed. Optical interconnection technology using an optical waveguide facilitates high-density integration with various optical devices on the same substrate, and has a technical advantage in terms of alignment and stability.

As a matrix material for optical signal transmission in various optical components as described above, studies for using polymers in place of conventional silica have been actively conducted. As a matrix material, a polymer material can be easily applied to various fabrication processes, and fabrication of a waveguide using the polymer material can be implemented relatively easily, which is a suitable material for realizing a low-cost fabrication process. The polymer optical waveguide generally has a multi-layered structure of a core layer, which is a light waveguide layer for optical propagation, and an upper and a lower cladding layer, which have a lower refractive index than a core layer. Therefore, the polymer optical waveguide has excellent chemical resistance and heat resistance The optical loss must be small.

As described above, optical communication devices using polymers have been actively researched by many organizations because they can be manufactured at low cost because it is possible to use inexpensive materials, simple and easy manufacturing process, and mass production technology. In order for the optical communication device using such a polymer to be industrially applicable, it is required to have excellent solubility in erbium, high transparency in the optical communication wavelength band, and heat resistance (300 to 350 ° C. or more) that can withstand thermal history during component mounting. However, it is difficult to satisfy the three characteristics of a polymer material as a matrix material at the same time.

One embodiment of the present invention provides a core composition for forming a core layer of an optical waveguide device having a core composition ratio for a high optical signal optical amplifier and excellent heat resistance.

Another embodiment of the present invention provides an optical waveguide element comprising the core layer.

One embodiment of the present invention relates to a method for producing an optical fiber comprising the steps of: (a) irradiating light containing fluorine-substituted acrylic monomer, (b) an erbium complex compound, (c) a cyclic structure- A core composition for a waveguide device is provided.

In another embodiment of the present invention, the core composition for optical waveguide comprises (a) 1 to 70% by weight of a fluorine-substituted acrylic monomer, (b) 1 to 30% by weight of an erbium complex, (c) 1 to 70% by weight of a liquid type monomer, (d) 1 to 30% by weight of a siloxane-based compound, and (e) 0.5 to 5% by weight of a reaction initiator.

In another embodiment of the present invention, the fluorine-substituted acrylic monomer may be represented by the following formula (1) or (2).

 [Chemical Formula 1]

(2)

In the above formulas,

또는

이며, A is

or

Lt;

R ¹ is each independently hydrogen, -OH or a C 1 -C 10 alkyl group, R ² is hydrogen, R ³ is each independently hydrogen or fluoro, R ⁴ is each independently hydrogen or fluoro, R ⁵ To R ⁷ are each independently hydrogen, fluoro, -OH, -CF ₃ or a C 1 -C 10 alkyl group, with the proviso that R ⁵ to R ⁷ Is fluoro, m is an integer of 0 to 5, and n is 0 to 15.

In another embodiment of the present invention, the fluorosubstituted acrylic monomer is selected from the group consisting of 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl (meth) acrylate , 3,3,4,4,5,5,6,6,7,8,8,8-Dodecafluoro-7- (trifluoromethyl) octyl (meth) acrylate, 3,3,4 , 4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-heneicosafluorododecyl (meth) acrylate, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,12,12,12-Eicosa fluoro-11- (trifluoro Methyl) dodecyl (meth) acrylate, 3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl (meth) Acrylate, 2,2,3,3,4,4,4-heptafluorobutyl (meth) acrylate, 4,4,5,5,6,6,7,7,8,8,9,9 , 10,11,11,11-hexadecafluoro-2-hydroxy-10- (trifluoromethyl) undecyl (meth) acrylate, 3,3,4,4,5,5,6,6 , 7,7,8,8,9,10,10,10-hexadecafluoro-9- (trifluoromethyl) decyl (meth) acrylate, 2,2,3,4,4,4-hexa Fluorobutyl (meta ) Acrylate, 1,1,1,3,3,3-hexafluoroisopropyl (meth) acrylate, 4,4,5,5,6,7,7,7-octafluoro-2-hyde (Trifluoromethyl) heptyl methacrylate, 2,2,3,3,4,4,5,5-octafluoropentyl (meth) acrylate, 2,2,3,3-tetra (Meth) acrylate, 2,2,3,3-pentafluoropropyl (meth) acrylate, 2,2,3,3-butafluoropropyl (meth) acrylate, 3,3 , 4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-2-hydroxy-6-octyl (meth) acrylate, 3,3,4,4, 5,6,6,7,7,8,8,8-tridecafluorooctyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 1,1,1 2 - [(1 ', 1', 1 '-trifluoro-2-hydroxy-4-methyl-5-pentyl (Trifluoromethyl) -2'-hydroxy) propyl] -3-norbornyl (meth) acrylate, 4,4,5,5,6,6,7,7,8,9,9, 9-degree 1H, 1H, 2H, 2H-perfluorodecyl (meth) acrylate, 4,4,5,5,5-hexafluoroisopropyl (meth) acrylate, decafluoro-2- 6,6,7,7,8,8,9,9,9-tridecafluoro-2-hydroxynonyl (meth) acrylate, and combinations thereof.

In another embodiment of the invention, the erbium complex is selected from the group consisting of erbium (III) -tris (6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionate (III) bromide, erbium (III) chloride, erbium (III) fluoride, erbium (III) iodide, erbium (III) nitrate, pentahydrate, erbium Erbium (III) sulfate, erbium (III) acetate hydrate, erbium (III) acetylacetonate hydrate, erbium (III) oxalate hydrate, erbium (III) phosphate hydrate and combinations thereof.

In another embodiment of the present invention, the cyclic structure-containing normal temperature liquid-phase monomer is a substituted or unsubstituted C6 to C20 cyclic ring, a substituted or unsubstituted C3 to C20 heterocyclic ring, a substituted or unsubstituted C6 to C20 aryl ring And a substituted or unsubstituted C3 to C20 heteroaryl ring, and combinations thereof, and includes at least one (meth) acrylic group.

(Meth) acrylate, benzyl 2-propyl (meth) acrylate, ethyleneglycolphenyl ether (hereinafter referred to as " (Meth) acrylate, 2-hydroxyethyl-3-phenoxypropyl (meth) acrylate, benzyl (meth) acrylate, phenyl methacrylate, , Phenylbutyl (meth) acrylate, styrene, and combinations thereof.

In another embodiment of the present invention, the siloxane-based compound is selected from the group consisting of methacryloxypropyl terminated polydimethylsiloxane, (3-acryloxy-2-hydroxypropoxypropyl) terminated polydimethylsiloxane, (methacryloxypropyl) (3-acryloxy-2-hydroxypropoxypropyl) methylsiloxane-dimethylsiloxane copolymer, a methacryloxypropyl T-structure (methacryloxypropylmethylsiloxane-dimethylsiloxane copolymer) Siloxane, acryloxypropyl T-structure siloxane, acryloxy-terminated ethylene oxide-dimethylsiloxane-ethylene oxide ABA block copolymer, methacryloxypropyl terminated branched polydimethylsiloxane, acryloisobutyl poly octahead laurylsesquioxane , Methacryloyl isobutyl poly octahead lauryl silsesquioxane, methacrylate cyclohexyl polyoctaheadular silsesquioxane, methacrylic Methoxyethyl methacrylate, isobutyl poly octahead lauryl silsesquioxane, methacrylate ethyl poly octahead lauryl silsesquioxane, methacryl ethyl poly octahead lauryl silsesquioxane, methacrylate isooctyl poly octahead lauryl silsesquioxane, Methacryloylphenyloctahydrosalicylsuccinic acid, methacryloylpolyhetahelyl silsesquioxane, acrylopolyioctahedral silsesquioxane, and combinations thereof. ≪ Desc / Clms Page number 7 >

In another embodiment of the present invention, the reaction initiator may be selected from a benzophenone-based compound which is a radical polymerization type, an acetophenone-based compound, a benzoin ether-based compound, a thioxanthone-based compound and a combination thereof.

In another embodiment of the present invention, the composition may additionally comprise one or more from the group consisting of solvents, acrylic oligomers, defoamers, thickeners and flow control agents.

In another embodiment of the invention the solvent is selected from the group consisting of ethanol, methanol tetrahydrofuran, acetone, methyl ethyl ketone, ethyl ether, dimethyl ether, dichloromethane, tetrachloromethane, chloroform, benzene, toluene, . ≪ / RTI >

In another embodiment of the present invention, the acrylate oligomer is selected from an epoxy acrylate oligomer, a urethane acrylate oligomer, a polyester acrylate oligomer, and combinations thereof, and comprises at least one acrylate group.

In another embodiment of the present invention, there is provided an optical waveguide element comprising a core layer made from the core composition.

The core composition of the present invention has an advantage of ensuring high transparency in the optical communication wavelength band, minimizing the optical loss of the waveguide, increasing the optical amplification factor, and further providing a core layer excellent in heat resistance.

FIG. 1 is a scanning electron microscope (SEM) photograph of the core pattern prepared in Production Example 1. FIG.
2 is a SEM photograph of the core pattern prepared in Production Example 2. Fig.
3 is a SEM photograph of the core pattern prepared in Production Example 3. FIG.
FIG. 4 is a TGA (thermogravimetric analysis) result of the core polymer thin films prepared in Production Example 1 and Comparative Example 1.
FIG. 5 shows TGA results of the core polymer thin films prepared in Production Example 2 and Comparative Example 2. FIG.
6 shows TGA results of the core polymer thin films prepared in Preparative Example 3 and Comparative Example 3. FIG.
FIG. 7 shows an EPMA (electron probe micro-analyzer) mapping picture of the core polymer thin film prepared in Production Example 4. FIG.
FIG. 8 shows TGA results of the core polymer thin film prepared in Example 4. FIG.
9 is an EPMA mapping photograph of the core polymer thin film prepared in Example 5. FIG.
10 shows the TGA results of the core composition prepared in Example 5. Fig.
11 shows EPMA mapping photographs of the core polymer thin film prepared in Example 6. Fig.
12 shows the TGA results of the core composition prepared in Example 6. Fig.
13 shows EPMA mapping photographs of the core polymer thin film prepared in Example 7. FIG.
14 shows the TGA results of the core composition prepared in Example 7. Fig.
15 is an EPMA mapping photograph of the core polymer thin film prepared in Comparative Example 4. FIG.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings, which will be readily apparent to those skilled in the art to which the present invention pertains. The present invention may be embodied in many different forms and is not limited to the embodiments described herein.

Unless otherwise specified herein, "substituted" means that at least one hydrogen atom is replaced by a halogen atom (fluoro, Cl, Br, I), a hydroxy group, a C1-20 alkoxy group, a nitro group, a cyano group, A thio group, an ester group, an ether group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, an acid anhydride, an amide group, an azo group, an azido group, an amidino group, a hydrazino group, a hydrazino group, a carbonyl group, , A C1-20 alkyl group, a C2-20 alkenyl group, a C2-20 alkynyl group, a C6-30 aryl group, a C2-20 cycloalkyl group, a C2-20 cycloalkenyl group, a C2-20 cycloalkynyl group, a C2-20 heterocycloalkyl group , C2-20heterocycloalkenyl group, C2-20heterocycloalkynyl group, C2-20heteroaryl group, or a combination thereof.

Also, unless otherwise specified herein, "hetero" means that at least one heteroatom of N, O, S and P is included in the ring group.

The present invention relates to a core composition for producing a core layer in an Er-doped waveguide optical amplifier.

The present invention relates to an optical waveguide core comprising (a) a fluorine-substituted acrylic monomer, (b) an erbium complex, (c) a cyclic structure-containing room temperature liquid phase monomer, (d) a siloxane- Lt; / RTI >

(a) Fluoro  Substituted acrylic Monomer

A typical cause of optical loss on the polymer optical waveguide is due to absorption and scattering. Absorption leads to optical loss due to absorption of harmonic vibration inherent in the material in the near infrared region currently used in optical communication systems. On the other hand, scattering is caused by the intrinsic property of the material, and light loss occurs mainly due to Rayleigh scattering due to the difference in density at the interface between the core layer and the cladding layer.

In order to prevent light propagation loss due to Rayleigh scattering, the present invention provides a polymer having a low refractive index as a core layer by using an acrylic monomole in which hydrogen is substituted with fluorine.

In one embodiment of the present invention, the fluorine-substituted acrylic monomer may be represented by the following formula (1) or (2).

[Chemical Formula 1]

(2)

또는

이며, R¹은 각각 독립적으로 수소, -OH 또는 C1-C10 알킬기이며,R²는 수소이며, R³은 각각 독립적으로 수소 또는 플루오로이며, R⁴는 각각 독립적으로 수소 또는 플루오로이며, R⁵ 내지 R⁷은 각각 독립적으로 수소, 플루오로, -OH, -CF₃ 또는 C1-C10 알킬기이며(단, R⁵ 내지 R⁷ 중 적어도 하나 이상이 플루오로이며), m은 0 내지 5의 정수이며, n은 0내지 15이다. In the above formula, A is

or

And, R ¹ is hydrogen, -OH or C1-C10 alkyl group, each independently, R ² is hydrogen, R ³ is hydrogen or fluoro, each independently, R ⁴ is hydrogen or fluoro, each independently, R ⁵ to R ⁷ are each independently hydrogen, fluoro, -OH, -CF ₃ or C 1 -C 10 alkyl group (provided that at least one of R ⁵ to R ⁷ is fluoro), m is an integer of 0 to 5 And n is 0 to 15.

In one embodiment of the present invention, the fluorine-substituted acrylic monomer is 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl (meth) acrylate 3,3,4,4,5,5,6,6,7,8,8,8-dodecafluoro-7- (trifluoromethyl) octyl (meth) acrylate, 3,3,4,4,5,5,6,6,7,8,8,8- 4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-heneicosafluorododecyl (meth) acrylate , 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,12,12,12-Eicosa fluoro-11- (trifluoro (Meth) acrylate, 3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl (meth) acrylate, Acrylate, 2,2,3,3,4,4,4-heptafluorobutyl (meth) acrylate, 4,4,5,5,6,6,7,7,8,8,9, (Trifluoromethyl) undecyl (meth) acrylate, 3,3,4,4,5,5,6,6-hexafluoro-2- 6,7,7,8,8,9,10,10,10-hexadecafluoro-9- (trifluoromethyl) decyl (meth) acrylate, 2,2,3,4,4,4- Hexafluorobutyl ( L) acrylate, 1,1,1,3,3,3-hexafluoro-isopropyl (meth) acrylate,

4,4,5,5,6,7,7,7-octafluoro-2-hydroxy-6- (trifluoromethyl) heptyl methacrylate, 2,2,3,3,4,4, Pentafluoropropyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) (Meth) acrylate, 2,2,3,3-butafluoropropyl (meth) acrylate, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro 2-hydroxy-6-octyl (meth) acrylate, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl (meth) (Meth) acrylate, 1,1,1-trifluoro-2- (trifluoromethyl) -2-hydroxy-4-methyl-5-pentyl (Meth) acrylate, 2 - [(1 ', 1', 1 '-trifluoro-2' - (trifluoromethyl) -2'- , 4,4,5,5,6,6,7,7,8,9,9,9-dodecafluoro-2-hydroxy-8- (trifluoromethyl) nonyl (meth) acrylate , 1H, 1H, 2H, 2H-perfluorodecyl (meth) acrylate, 4,4,5,5,6,6,7,7,8,8,9,9,9-tridecafluoro- 2-hydroxynonyl (meth) acrylate, and combinations thereof.

Particularly preferably, the following formula (1) or (2) may be the following compound.

The fluorine-substituted acrylic monomer provides a polymer having a low refractive index to prevent loss of the optical waveguide. The content of the fluorine-substituted acrylate monomer may be 1 to 70% by weight, preferably 10 to 60% by weight, more preferably 20 to 50% by weight, based on the total amount of the core composition. If the above numerical range is satisfied, the absorption loss in the near infrared region due to the overtone of CH bonds can be minimized.

(b) an erbium complex

It is understood that the erbium complex is well known to those skilled in the art so that it can be commercially purchased and used.

In one embodiment of the present invention, the erbium complex comprises erbium (III) -tris (6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl- Erbium (III) bromide, erbium (III) chloride, erbium (III) fluoride, erbium (III) iodide, erbium (III) nitrate pentahydrate, erbium Erbium (III) acetate hydrate, erbium (III) acetylacetonate hydrate, erbium (III) oxalate hydrate, erbium (III) phosphate hydrate and combinations thereof.

The content of the erbium complex may be 1 to 30 wt%, preferably 1 to 20 wt%, and more preferably 1 to 10 wt%, based on the total amount of the core composition. When the numerical range is satisfied, the optical amplification efficiency of the erbium-based near infrared region is excellent.

(c) Ring structure - containing room temperature liquid type Monomer

The present invention includes a ring structure-containing room temperature liquid phase monomer as an agent for improving the solubility of an erbium complex. Unlike conventional EDFA, EDWA requires doping of high concentration of erbium ions to obtain high amplification efficiency in a very short length. However, when the concentration of erbium ions is increased to increase the optical amplification, the aggregation of the erbium ions causes energy migration, upconversion, and excited state absorption, The intensity decreases sharply and causes a low optical amplification gain.

 To solve this problem, the erbium complex must be uniformly dissolved at the molecular level. The present invention relates to a monomer having excellent solubility in an erbium complex, which comprises a cyclic structure and a monomer in a liquid state at room temperature.

Wherein said ring structure is a substituted or unsubstituted C6 to C20 cyclic ring, a substituted or unsubstituted C3 to C20 heterocycle ring, a substituted or unsubstituted C6 to C20 aryl ring, a substituted or unsubstituted C3 to C20 heteroaryl ring . The cyclic structure-containing normal temperature liquid-phase monomer contains at least one (meth) acrylic group in order to participate in the polymerization reaction and be included as a part of the polymer matrix.

In one embodiment of the present invention, the cyclic structure-containing room temperature liquid-phase monomer is a monomer having a structure represented by the following structural formula: tetrahydrofurfuryl (meth) acrylate, peryl (meth) acrylate, benzyl 2-propyl (Meth) acrylate, benzyl (meth) acrylate, phenyl methacrylate, 2-phenylethyl (meth) acrylate, phenylpropyl (meth) acrylate, (Meth) acrylate, phenylbutyl (meth) acrylate, styrene, and combinations thereof.

<Example of cyclic structure-containing room temperature liquid phase monomer compound>

The content of the cyclic structure-containing normal temperature liquid phase monomer may be 1 to 70% by weight, preferably 10 to 60% by weight, more preferably 20 to 50% by weight, based on the total amount of the core composition. When the numerical range is satisfied, it is possible to minimize the decrease in the optical amplification efficiency due to the non-emission disappearance due to the erbium flocculation phenomenon.

(d) Silkworm  compound

The polymer of the optical waveguide of the optical amplifier needs not only the excellent solubility in erbium, the high transparency in the optical communication wavelength band, but also the heat resistance (300 to 350 ° C. or more) that can withstand the thermal history in the component mounting.

To ensure such heat resistance, the present invention includes a siloxane-based compound. In one embodiment of the present invention, polysiloxane and polysilsesquioxane compounds may be used as the siloxane compound. Since the siloxane-based compound has a siloxane structure similar to silica in the main chain structure, it has a low optical loss and is excellent in heat resistance and functions as a heat resistance-increasing agent.

The siloxane-based compound may be represented by the following formulas (3) to (10).

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

In the above formula (7), R is i-butyl.

[Chemical Formula 8]

In the above formula (8), R is ethyl, i-butyl, i-octyl or phenyl.

[Chemical Formula 9]

In the above formula (9), R is ethyl, i-butyl, i-octyl or phenyl.

[Chemical formula 10]

또는

이다.
In Formula 10, R is

or

to be.

The content of the siloxane-based compound may be 1 to 30% by weight, preferably 1 to 20% by weight, based on the total amount of the core composition for optical waveguide elements. When the above numerical range is satisfied, a SiO ₂ (silica) coating is formed at a high temperature and the heat resistance is excellent.

(e) Reaction initiator

As the reaction initiator, a benzophenone-based compound such as a radical polymerization type, an acetophenone-based compound, a benzoin ether-based compound, a thioxanthone-based compound, and the like can be used commercially and commercially available to those having ordinary skill in the art And may be used alone or in combination of two or more. Examples are IRGACURE 184, IRGACURE 500, DAROCUR 1173, IRGACURE 2959, DAROCUR MB fluoro, IRGACURE 754, IRGACURE 651, IRGACURE 369, IRGACURE 907, IRGACURE 1300, DAROCUR TPO, DAROCUR 4265, IRGACURE 819, IRGACURE 819DW , IRGACURE 2022, IRGACURE 2100, IRGACURE 784, IRGACURE 250, and the like.

The content of the reaction initiator may be 0.5 to 5 wt%, preferably 0.5 to 3 wt%, based on the total amount of the core composition for optical waveguide elements. When the above numerical range is satisfied, flexibility and adhesion force are excellent.

In addition to the components (a) to (e), the core composition may further comprise at least one substance selected from the group consisting of solvents, acrylic oligomers, thickeners and flow control agents.

(f) Solvent

Since the core composition of the present invention contains a cyclic structure-containing normal temperature liquid-phase monomer, the use of an additional solvent is not necessary, When the components constituting the composition are not readily soluble in the cyclic structure-containing normal temperature liquid type monomer, a solvent may additionally be contained as an additive. Examples of the solvent include ethanol, methanol tetrahydrofuran, acetone, methyl ethyl ketone, ethyl ether, dimethyl ether, dichloromethane, tetrachloromethane, chloroform, benzene, toluene, xylene, .

(g) Acrylic Oligomer

The core composition may further comprise an acrylic oligomer. The acrylic oligomer may be an epoxy acrylate oligomer having at least one acrylate group, a urethane acrylate oligomer, a polyester acrylate oligomer, or the like, which is commercially available to those skilled in the art. And may be used singly or in combination. Examples of the acrylic oligomer include CEC Corporation's EBECRYL 230, EBECRYL 242, EBECRYL 264, EBECRYL 265, EBECRYL 270, EBECRYL 284, EBECRYL 1290, EBECRYL 4833, EBECRYL 4858, EBECRYL 4883, EBECRYL 5129, EBECRYL 8210, EBECRYL 8296, EBECRYL 8301- R, EBECRYL 8309, EBECRYL 8311, EBECRYL 8402, EBECRYL 8405, EBECRYL 8411, EBECRYL 8412, EBECRYL 8414, EBECRYL 8465, EBECRYL 8501, EBECRYL 8701, EBECRYL 8702, EBECRYL 8800, EBECRYL, EBECRYL 8800-20R, EBECRYL 8804, EBECRYL 8807 , EBECRYL 8808, EBECRYL 220, EBECRYL 4827, EBECRYL 4849, EBECRYL 80, EBECRYL 81, EBECRYL 450, EBECRYL 657, EBECRYL 809, EBECRYL 810, EBECRYL 812, EBECRYL 830, EBECRYL 838, EBECRYL 870, EBECRYL 885, EBECRYL 888, 889, EBECRYL 891, EBECRYL 893, EBECRYL 600, EBECRYL 605, EBECRYL 608, EBECRYL 3200, EBECRYL 3201, EBECRYL 3300, EBECRYL 3415, EBECRYL 3500, EBECRYL 3600, EBECRYL 3700, EBECRYL 3701, EBECRYL 3702, EBECRYL 3703, EBECRYL 3708, EBECRYL 3720, and the like.

(h) Others

Examples of the antifoaming agent include, but are not limited to, a mineral oil type antifoaming agent, a silicone type antifoaming agent, a polymer type antifoaming agent and the like. As the water-soluble thickening agent, potassium carbomer, potassium chloride, etc. may be used, but the present invention is not limited thereto. As the fluidity adjusting agent, any additive capable of optimally adjusting the flow characteristics can be used, so a detailed description thereof will be omitted herein.

Example

&Lt; Example 1 >

6.5 g of 2,2,3,3,4,4,5,5-octafluoropentyl acrylate, 6 g of erbium (III) -tris (6,6,7,7,8,8,8-heptafluoro 0.5 g of 2,2-dimethyl-3,5-octanedionate, 2.0 g of tetrahydrofurfuryl acrylate, 1.0 g of acrylopolyioctahedral silsesquioxane and 0.1 g of DAROCUR 4265 at a rate of 12 rpm For a period of time to prepare a uniform core composition. The core composition was used to prepare a polymer thin film of the core layer by a soft lithography method.

&Lt; Example 2 >

5.5 g of 2,2,3,3,4,4,4-heptafluorobutyl acrylate, 2.0 g of erbium (III) tri-fluoromethanesulfonate 0.5 g of furfuryl acrylate, 2.0 g of silsesquioxane, 0.1 g of DROCUR 4265 and 0.5 g of EBECRYL 230 were stirred at a speed of 500 rpm for 12 hours to prepare a uniform core composition. Polymer thin films of the core layer were prepared by the micro molding in capillaries method using the core composition.

&Lt; Example 3 >

4.5 g of 2,2,3,4,4,4-hexafluorobutyl methacrylate, 0.5 g of erbium (III) acetylacetonate hydrate, 0.5 g of acetylacetonate hydrate, 2.0 g of ethylene glycol phenyl ether acrylate, 3.0 g of methacryloxypropyl terminated polydimethylsiloxane and 0.1 g of DROCUR 4265 were stirred at 500 rpm for 12 hours to prepare a homogeneous core composition. Polymer thin films of the core layer were prepared by the capillary force micro molding method using the core composition.

<Example 4>

3.5 g of 4,4,5,5,6,7,7,7-octafluoro-2-hydroxy-6- (trifluoromethyl) heptyl methacrylate, 0.5 g of erbium (III) oxalate hydrate 5.0 g of 2-hydroxy-3-phenoxypropyl acrylate, 1.0 g of methacryloxypropyl T-structured siloxane, 0.1 g of IRGACURE 819 and 0.5 g of tetrahydrofuran as a solvent were mixed and stirred at 500 rpm for 12 hours To prepare a homogeneous uniform core composition, and polymerized to prepare a polymer thin film of the core layer.

&Lt; Example 5 >

2.5 g of 2,2,3,3,3-pentafluoropropylacrylate, 0.5 g of erbium (III) chloride, 6.0 g of benzyl methacrylate, 1.0 g of methacrylate isooctyl polyoctahedral silsesquioxane And IRGACURE 819 (0.1 g) were stirred at 500 rpm for 12 hours to prepare a uniform core composition and polymerized to prepare a polymer thin film of the core layer.

&Lt; Example 6 >

1.5 g of 1,1,1,3,3,3-hexafluoroisopropyl methacrylate, 0.5 g of erbium (III) nitrate pentahydrate, 7.0 g of benzyl 2-propyl acrylate, 0.5 g of acryloyl isobutyl poly octa 1.0 g of headless salsilsquioxane, 0.1 g of IRGACURE 819 and 0.5 g of EBECRYL 3702 were stirred at 500 rpm for 12 hours to prepare a homogeneous core composition and polymerized to prepare a polymer thin film of the core layer.

&Lt; Example 7 >

3.5 g of 1,1,1-trifluoro-2- (trifluoromethyl) -2-hydroxy-4-methyl-5-pentyl methacrylate, 1.0 g of erbium (III) phosphate hydrate, 3.5 g of methacrylate, 1.5 g of methacrylate cyclohexyl polyoctahedral silsesquioxane and 0.1 g of DAROCUR 4265 were stirred at 500 rpm for 12 hours to prepare a homogeneous core composition, .

&Lt; Comparative Example 1 &

A core polymer thin film was prepared in the same manner as in Example 1, except that acrylo poly octahedra salce sesquioxane was used as the siloxane-based compound.

&Lt; Comparative Example 2 &

A core polymer thin film was prepared in the same manner as in Example 2, except that methacryloyl polyhexafarrhylsilsesquioxane was used as the siloxane-based compound.

&Lt; Comparative Example 3 &

A core polymer thin film was prepared in the same manner as in Example 3, except that methacryloxypropyl terminated polydimethylsiloxane was used as the siloxane compound.

&Lt; Comparative Example 4 &

A core polymer thin film was prepared in the same manner as in Example 4, except that 2-hydroxy-3-phenoxypropyl acrylate was used as a solubility enhancer of erbium ion.

<Experimental Example 1>

SEM (Scanning Electron Microscope) was taken of the core patterns prepared in Examples 1 to 3, and TGA (thermogravimetric analysis) was measured on the core thin film polymers of Examples 1 to 3 and Comparative Examples 1 to 3. Figs. 1 to 3 are SEM photographs of core patterns of Examples 1 to 3. Fig.

FIGS. 4 to 6 show that Examples 1 to 3 have higher thermal decomposition temperatures than Comparative Examples 1 to 3, respectively, showing that the heat resistance of the core layer is improved by including the siloxane-based compound.

<Experimental Example 2>

EPMA (Electron Probe Micro Analyzer) mapping photographs of the erbium ions of the polymer thin films prepared using the core compositions prepared in Examples 4 to 7 and the transmittance of the polymer matrix were measured.

As a result of EPMA and permeability analysis of the polymer thin film prepared in Example 4, it was confirmed that the erbium ion was uniformly dispersed in the polymer matrix (FIG. 7) and the transmittance reduction by the polymer matrix was less than 2% (FIG.

As a result of EPMA and permeability analysis of the polymer thin film prepared in Example 5, it was confirmed that the erbium ion was uniformly dispersed in the polymer matrix (FIG. 9) and the decrease of the permeability by the polymer matrix was less than 2% (FIG.

As a result of EPMA and permeability analysis of the polymer thin film prepared in Example 6, it was confirmed that the erbium ion was uniformly dispersed in the polymer matrix (FIG. 11) and the transmittance reduction by the polymer matrix was less than 2% (FIG.

As a result of EPMA and permeability analysis of the polymer thin film prepared in Example 7, it was confirmed that the erbium ion was uniformly dispersed in the polymer matrix (FIG. 13) and the transmittance reduction by the polymer matrix was less than 2% (FIG. 14).

As a result of EPMA analysis of the polymer thin film prepared in Comparative Example 4, it was confirmed that the erbium ion was dispersed unevenly in the polymer matrix (FIG. 15).

While the present invention has been described in connection with what is presently considered to be the most practical and preferred embodiment, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and similarities.

Therefore, it should be understood that the above-described embodiments are provided so that those skilled in the art can fully understand the scope of the present invention. Therefore, it should be understood that the embodiments are to be considered in all respects as illustrative and not restrictive, The invention is only defined by the scope of the claims.

Claims (13)

A core composition for an optical amplifier comprising the following components:
(a) 1 to 70% by weight of fluorine-substituted acrylic monomers;
(b) 5 to 30% by weight of an erbium complex compound;
(c) 20 to 50% by weight of cyclic structure-containing normal temperature liquid phase monomer;
(d) 1 to 30% by weight of a siloxane-based compound; And
(e) 0.5 to 5% by weight of a reaction initiator. delete The core composition for an optical amplifier according to claim 1, wherein the fluorine-substituted acrylic monomer is represented by the following formula (1) or (2):
[Chemical Formula 1]

(2)

In the above formulas,
A is

or

Lt;
R ¹ is independently hydrogen, -OH or a C 1 -C 10 alkyl group,
R ² is hydrogen,
R &lt; ³ &gt; are each independently hydrogen or fluoro,
R &lt; ⁴ &gt; are each independently hydrogen or fluoro,
R ⁵ to R ⁷ are each independently hydrogen, fluoro, -OH, -CF ₃ or C 1 -C 10 alkyl group, provided that at least one of R ⁵ to R ⁷ is fluoro,
m is an integer of 0 to 5,
n is from 0 to 15; The fluorine-substituted acrylic monomer according to claim 1, wherein the fluorine-substituted acrylic monomer is 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl (meth) acrylate, 3 , 3,4,4,5,5,6,6,7,8,8,8-Dodecafluoro-7- (trifluoromethyl) octyl (meth) acrylate, 3,3,4,4 , 5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-heneicosafluorododecyl (meth) acrylate, 3, 3, 4, 5, 5, 6, 6,7,7,8,8,9,9,10,10,11,12,12,12-Eicosa fluoro-11- (trifluoromethyl) Dodecyl (meth) acrylate, 3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl (meth) acrylate , 2,2,3,3,4,4,4-heptafluorobutyl (meth) acrylate, 4,4,5,5,6,6,7,7,8,8,9,9,10 , 11,11,11-hexadecafluoro-2-hydroxy-10- (trifluoromethyl) undecyl (meth) acrylate, 3,3,4,4,5,5,6,6,7 , 7,8,8,9,10,10,10-hexadecafluoro-9- (trifluoromethyl) decyl (meth) acrylate, 2,2,3,4,4,4-hexafluoro Butyl (meth) acrylate Hexafluoroisopropyl (meth) acrylate, 4,4,5,5,6,7,7,7-octafluoro-2-hydroxy- Octafluoropentyl (meth) acrylate, 2,2,3,3-tetrafluoro (meth) acrylate, 2,2,3,3,4,4,5,5-octafluoropentyl (Meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, 2,2,3,3-butafluoropropyl (meth) acrylate, 3,3,4 , 4,5,5,6,6,7,7,8,8,8-tridecafluoro-2-hydroxy-6-octyl (meth) acrylate, 3,3,4,4,5, 5,6,6,7,7,8,8,8-tridecafluorooctyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 1,1,1-tri Acrylate, 2 - [(1 ', 1', 1 '-trifluoro-2'-fluoro-2- (Trifluoromethyl) -2'-hydroxy) propyl] -3-norbornyl (meth) acrylate, 4,4,5,5,6,6,7,7,8,9,9,9- Dodecafluor (Meth) acrylate, 1H, 1H, 2H, 2H-perfluorodecyl (meth) acrylate, 4,4,5,5,6,6 , 7,7,8,8,9,9,9-tridecafluoro-2-hydroxynonyl (meth) acrylate, and combinations thereof. The method of claim 1, wherein the erbium complex is selected from the group consisting of erbium (III) -tris (6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionate, erbium (III) bromide, erbium (III) chloride, erbium (III) fluoride, erbium (III) iodide, erbium (III) nitrate, pentahydrate, erbium (III) Wherein the core composition is selected from sulfite, erbium (III) acetate hydrate, erbium (III) acetylacetonate hydrate, erbium (III) oxalate hydrate, erbium (III) phosphate hydrate and combinations thereof. The process of claim 1, wherein the cyclic structure-containing normal temperature liquid-phase monomer is a substituted or unsubstituted C6 to C20 cyclic ring, a substituted or unsubstituted C3 to C20 heterocyclic ring, a substituted or unsubstituted C6 to C20 aryl ring, Or an unsubstituted C3 to C20 heteroaryl ring, and combinations thereof, and comprises at least one (meth) acrylic group. The method of claim 6, wherein the cyclic structure-containing normal temperature liquid-phase monomer is at least one selected from the group consisting of tetrahydrofurfuryl (meth) acrylate, peryl (meth) acrylate, benzyl 2-propyl (meth) acrylate, ethylene glycol phenyl ether (Meth) acrylate, phenyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxypropyl Butyl (meth) acrylate, styrene, and combinations thereof. The composition of claim 1 wherein said siloxane-based compound is selected from the group consisting of methacryloxypropyl terminated polydimethylsiloxane, (3-acryloxy-2-hydroxypropoxypropyl) terminated polydimethylsiloxane, (methacryloxypropyl) (3-acryloxy-2-hydroxypropoxypropyl) methylsiloxane-dimethylsiloxane copolymer, methacryloxypropyl T-structure siloxane, acrylic (methacryloxypropyl) Oxypropyl T-structure siloxane, acryloxy-terminated ethylene oxide-dimethylsiloxane-ethylene oxide ABA block copolymer, methacryloxypropyl terminated branched polydimethylsiloxane, acryloisobutyl poly octahead laurylsesquioxane, methacryl Isobutyl poly octahead lauryl silsesquioxane, methacrylate cyclohexyl poly octahead lauryl silsesquioxane, methacrylate isobutyl Methacrylate ethyl polyacrylate, polyacrylate polyacrylate, polyacrylate polyacrylate, polyacrylate polyacrylate, polyacrylate polyacrylate, polyacrylate polyacrylate, polyacrylate polyacrylate, A core composition for an optical amplifier, which is selected from octahead laurylsuccioxane, methacrylphenyl polyoctahead laurylsilsesquioxane, methacryloylpolyoxyhexalaurylsilsesquioxane, acrylopolyioctahedral laurylsilsesquioxane, and combinations thereof. . The core composition for an optical amplifier according to claim 1, wherein the reaction initiator is a radical polymerization type selected from benzophenone compounds, acetophenone compounds, benzoin ether compounds, thioxanthone compound, and combinations thereof. The core composition for an optical amplifier according to claim 1, wherein the composition further comprises at least one member selected from the group consisting of a solvent, an acrylate oligomer, an antifoaming agent, an accelerator, and a flow control agent.  The method of claim 10, wherein the solvent is selected from the group consisting of ethanol, methanol tetrahydrofuran, acetone, methyl ethyl ketone, ethyl ether, dimethyl ether, dichloromethane, tetrachloromethane, chloroform, benzene, toluene, xylene, &Lt; / RTI &gt;  The core composition for an optical amplifier according to claim 10, wherein the acrylate oligomer is selected from an epoxy acrylate oligomer, a urethane acrylate oligomer, a polyester acrylate oligomer and a combination thereof, and comprises at least one acrylate group. An optical amplifier comprising a core layer made from the core composition according to claim 1.

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